We have investigated the stability and electronic properties of GaN nanowires photocathode based on first-principle calculations. The most stable adsorption configuration of Cs adatoms on the (001) surface of [001]-oriented GaN nanowires changes accordingly as Cs coverage increases. The work function of Cs-only-covered surface falls off with increasing Cs coverage. For the nanowire surface covered with either excessive or minor Cs coverage, the work function surprisingly increases slightly after O activation; however, for Cs coverage of 0.5 (monolayer) ML and 0.75 ML, O activation process still works for the nanowires photocathode. A downward band bending region is formed after Cs adsorption and will further bend downward after O adsorption only for models with Cs coverage of 0.5 ML and 0.75 ML. The optimized atomic ratio of Cs/O is 3:1. The diversification of the band structures is mainly attributed to the orbital hybridization between Cs-5 s, Cs-5p, O-2p states and Ga-4 s, N-2p states.